CN101874087A - Water-based metal-surface-treating agent - Google Patents
Water-based metal-surface-treating agent Download PDFInfo
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- CN101874087A CN101874087A CN200880117813A CN200880117813A CN101874087A CN 101874087 A CN101874087 A CN 101874087A CN 200880117813 A CN200880117813 A CN 200880117813A CN 200880117813 A CN200880117813 A CN 200880117813A CN 101874087 A CN101874087 A CN 101874087A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
An agent for metal surface treatment comprising a polymer (P) which is a polymer having, in the molecule, monomer units derived from a (meth)acrylic ester (A) represented by the general formula (I): [wherein R1 represents hydrogen or methyl and R2 represents a group represented by the general formula (II): (wherein R3, R4, and R5 each independently represents hydrogen, hydroxy, or C1-3 alkyl)] and has a glass transition temperature of 0-70 DEG C, an emulsifying agent, and water, the polymer (P) having been dispersed with the emulsifying agent. This treating agent has excellent storage stability and can form a coating film excellent in unsusceptibility to deterioration by ultraviolet, alkali resistance, acid resistance, processability, and permeability.
Description
Technical field
The present invention relates to have excellent storage stability and can form the water-based metal-surface-treating agent of the good tunicle of UV resistant deterioration, alkali resistance, acid resistance, processibility and the tunicle transparency.
Background technology
Usually, as good to the binding property of metal material surface and give the technology of metal material surface erosion resistance and processibility etc., generally be metal material surface implement to be utilized contain organic resin and chromic acid, dichromic acid or their salt method, but the corresponding type chromate-free of the environment organic resin tunicle processing etc. of bridging property metal that now chromium is replaced with other is just by in practical application as the resin chromate treating of the treatment solution of main component.
As the chromate-free organic resin by membrane technology, the method of making the high-weatherability emulsifying agent is disclosed in the patent documentation 1, it is characterized in that, will contain the monomer composition emulsion polymerization of (methyl) acrylate, dialkyl group (methyl) acrylamide and tensio-active agent at least.
In addition, as the chromate-free organic resin by membrane technology, the method of making the particulate emulsifying agent is disclosed in the patent documentation 2, it is characterized in that, will contain (methyl) acrylate at least, be the vinylbenzene of 0.1～20 quality % and the monomer composition emulsion polymerization of tensio-active agent with respect to this (methyl) acrylate.
In addition, as the chromate-free organic resin by membrane technique, the sheet metal surface treatment agent that does not contain chromium is disclosed in the patent documentation 3, it is characterized in that, contain the metallic compound more than a kind or 2 kinds of aqueous resin that (A) have carboxyl and amido linkage, metallic compound that (B) is selected from Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, V, W, Mn and Ce and (C) silicon compound.
In addition, as the chromate-free organic resin by membrane technique, water-borne coatings is disclosed in the patent documentation 4, it contains resinous principle (A), solids component 100 mass parts that reach with respect to resinous principle (A) are the organic acid catalyst (C) of 0.01～10 mass parts, and above-mentioned resinous principle (A) is by making the specific nitrogenous free-radical polymerised unsaturated monomer (a) that contains 0.1～30 quality % with respect to the monomeric total amount that constitutes, the monomer mixture generation Raolical polymerizable of other the free-radical polymerised unsaturated monomer (c) that contains carboxyl free radical polymerizability unsaturated monomer (b) and 50～98.9 quality % of 1～20 quality % and obtaining.
Patent documentation 1: TOHKEMY 2000-327704 communique
Patent documentation 2: TOHKEMY 2000-327722 communique
Patent documentation 3: TOHKEMY 2003-201579 communique
Patent documentation 4: TOHKEMY 2006-152056 communique
Summary of the invention
But, can not say all methods stated and surface treatment agent and all have the performance that to use as the surrogate of resin chromic salt tunicle, have excellent storage stability and can form UV resistant deterioration, alkali resistance, acid resistance, processibility and the good tunicle of the tunicle transparency, thereby the surface treatment agent and the treatment process of above-mentioned condition can be synthetically satisfied in urgent expectation exploitation.
The objective of the invention is to, solve the problems referred to above that prior art exists, the water system surface treatment agent that has excellent storage stability and can form the good tunicle of UV resistant deterioration, alkali resistance, acid resistance, processibility and the tunicle transparency is provided.
The inventor has carried out wholwe-hearted research repeatedly in order to address these problems, found that, contain and have the polymkeric substance that polymerized unit and second-order transition temperature from (methyl) acrylate with ad hoc structure be 0～70 ℃ and the water system surface treatment agent of emulsifying agent in the molecule, have excellent storage stability, and can form UV resistant deterioration, alkali resistance, acid resistance, processibility and the good tunicle of the tunicle transparency, thereby finish the present invention.
Promptly, the present invention relates to a kind of metal conditioner, contain polymkeric substance (P), emulsifying agent and water, and polymkeric substance (P) is disperseed by this emulsifying agent, the polymerized unit that has (methyl) acrylate (A) of self-drifting (I) expression in the molecule of described polymkeric substance (P), and second-order transition temperature is 0～70 ℃
In the formula (I), R1 represents hydrogen atom or methyl, and R2 represents the represented group of general formula (II),
In the formula (II), R3, R4 and R5 represent the alkyl of hydrogen atom, hydroxyl or carbonatoms 1～3 independently of each other.
And, " from the polymerized unit of (methyl) acrylate (A) ", be meant that carbon-to-carbon double bond in (methyl) acrylate (A) is opened and the polymerized unit that forms, this reaches " from the polymerized unit of reactive emulsifier " for following " from the polymerized unit of silicon-containing monomer (B) ", " from α, the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) " and is suitable for too.
The polymerized unit that has the silicon-containing monomer (B) of self-drifting (III) expression in the molecule of preferred polymers (P),
In the formula (III), R6, R7 and R8 represent the alkyl of hydrogen atom, hydroxyl, carbonatoms 1～3, the alkoxyl group or carbonatoms 1～3 alkoxyl group carbonatoms 1～3 alkoxyl group of carbonatoms 1～3 independently of each other, X expression (IV) or the represented group of logical formula V
In the formula V, R9 represents that hydrogen atom or methyl, R10 represent the alkylene of carbonatoms 1～12.
Also has from α the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) in the molecule of preferred polymers (P).
From the ratio of the polymerized unit of (methyl) acrylate (A), be 0.1～50 mass parts preferably with respect to polymkeric substance (P) 100 mass parts.
From the ratio of the polymerized unit of silicon-containing monomer (B), be 0.5～2.0 mass parts preferably with respect to polymkeric substance (P) 100 mass parts.
The acid number of polymkeric substance (P) is preferably 5～40mgKOH/g.
Preferred above-mentioned metal conditioner contains softening agent (Q) 0.5～50 mass parts with respect to polymkeric substance (P) 100 mass parts.
Have at least 1 ester bond and/or at least 1 ehter bond in the molecule of preferred plasticizer (Q), more preferably softening agent (Q) is for being selected from 2,2,4-trimethylammonium-1, in 3-pentanediol mono isobutyrate, diethylene glycol monobutyl ether acetic ester, ethylene glycol monobutyl ether and the dipropylene glycol n-butyl ether at least a kind.
The invention effect
The water-based metal-surface-treating agent that has excellent storage stability of the application of the invention can form UV resistant deterioration, alkali resistance, acid resistance, processibility and the good tunicle of the tunicle transparency.
Embodiment
Water-based metal-surface-treating agent of the present invention need contain polymkeric substance (P), has the polymerized unit of (methyl) acrylate (A) of self-drifting (I) expression in the molecule of this polymkeric substance (P), and second-order transition temperature is 0～70 ℃,
In the formula (I), R1 represents hydrogen atom or methyl, and R2 represents the represented group of general formula (II),
In the formula (II), R3, R4 and R5 represent the alkyl of hydrogen atom, hydroxyl or carbonatoms 1～3 independently of each other.
The second-order transition temperature of polymkeric substance (P) need be 0～70 ℃, can keep alkali resistance, acid resistance, processibility and the tunicle transparency well thus.From the above point of view, this second-order transition temperature is preferably 10～60 ℃, more preferably 20～50 ℃.If second-order transition temperature is lower than 0 ℃, then not only alkali resistance and acid resistance significantly reduce, and add can not obtain man-hour needs by film hardness.Otherwise, if be higher than 70 ℃, stability in storage and add man-hour needed tunicle tracing property and significantly reduce then.
The effect that polymkeric substance (P) is given in (methyl) acrylate (A) unit is to follow the raising of alkali resistance, acid resistance and the processibility of second-order transition temperature rising.
And the R2 of (methyl) acrylate (A) needs only to be formed by saturated bond.If have unsaturated link(age), then, form chromophoric group, auxochromous group, thereby the UV resistant deterioration reduces significantly owing to free radical reaction takes place in ultraviolet ray.
About the definition of R3, R4 in the general formula (II) and R5, the alkyl of carbonatoms 1～3 comprises methyl, ethyl, propyl group and sec.-propyl.
As (methyl) acrylate (A),, can enumerate vinylformic acid norbornene ester, isobornyl acrylate, methacrylic acid norbornene ester and isobornyl methacrylate etc. though be not particularly limited.
The polymkeric substance that contains in the water-based metal-surface-treating agent of the present invention (P), the polymerized unit that has the silicon-containing monomer (B) of self-drifting (III) expression in the preferred molecule, thus, strengthened with the bounding force on metal to be treated surface thereby processibility improves, and alkali resistance and acid resistance improve.
In the formula (III), R6, R7 and R8 represent the alkyl of hydrogen atom, hydroxyl, carbonatoms 1～3, the alkoxyl group or carbonatoms 1～3 alkoxyl group carbonatoms 1～3 alkoxyl group of carbonatoms 1～3 independently of each other, X expression (IV) or the represented group of logical formula V
In the formula V, R9 represents that hydrogen atom or methyl, R10 represent the alkylene of carbonatoms 1～12.
Definition about R6, R7 in the general formula (III) and R8, the alkyl of carbonatoms 1～3 comprises methyl, ethyl, propyl group and sec.-propyl, the alkoxyl group of carbonatoms 1～3 comprises methoxyl group, oxyethyl group, propoxy-and isopropoxy, and carbonatoms 1～3 alkoxyl group carbonatoms 1～3 alkoxyl group comprises methoxy ethoxy etc.
R10 in the logical formula V is preferably the alkylene of carbonatoms 1～6, the more preferably alkylene of carbonatoms 1～4.
About the definition of R10 in the logical formula V,, can enumerate methylene radical, ethylidene, trimethylene, propylene, tetramethylene, hexa-methylene, eight methylene radical, decamethylene, ten dimethylenes etc. as alkylene.
As silicon-containing monomer (B), though be not particularly limited, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane etc.
In addition, have from α in the molecule of preferred polymers (P), the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) thus, becomes firmer with the bonding of metal to be treated surface, and acid resistance and processibility improve.
As α, β-ethylenically unsaturated carboxylic acids (C) though be not particularly limited, can be enumerated vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid, Ba Dousuan etc.
Combined amount about (methyl) acrylate (A), from the ratio of the polymer unit of (methyl) acrylate (A), with respect to polymkeric substance (P) 100 mass parts be preferably 0.1～50 mass parts, more preferably 0.5～45 mass parts, further be preferably 3.0～35 mass parts.Aforementioned proportion, if with respect to polymkeric substance (P) 100 mass parts less than 0.1 mass parts, then be difficult to show the additive effect of (methyl) acrylate (A), if surpass 50 mass parts, then be difficult to keep stability in storage.
Combined amount about silicon-containing monomer (B), from the ratio of the polymer unit of silicon-containing monomer (B), with respect to polymkeric substance (P) 100 mass parts be preferably 0.5～2.0 mass parts, more preferably 0.7～2.0 mass parts, further be preferably 1.0～2.0 mass parts.Aforementioned proportion, if with respect to polymkeric substance (P) 100 mass parts less than 0.5 mass parts, then be difficult to show the additive effect of silicon-containing monomer (B), if surpass 2.0 mass parts, then there is the tendency that reduces in stability in storage.
About α, the combined amount of β-ethylenically unsaturated carboxylic acids (C), the acid number from the polymkeric substance (P) of the polymer unit of (C) is preferably 5～40mgKOH/g, and more preferably 10～35mgKOH/g further is preferably 15～30mgKOH/g.If acid number less than 5mgKOH/g, then is difficult to show α, the additive effect of β-ethylenically unsaturated carboxylic acids (C).Otherwise, if surpass 40mgKOH/g, the then water-soluble enhancing of polymkeric substance (P), not only stability in storage reduces, and also there are the tendency of reduction in alkali resistance and acid resistance.
Under the situation of the emulsifying agent that when using reactive emulsifier, uses, also become the constituent of polymkeric substance (P) from the polymer unit of reactive emulsifier as manufacturing polymkeric substance (P).Under the situation of only using reactive emulsifier as emulsifying agent,, be preferably 0.5～5 mass parts, 1～3 mass parts more preferably with respect to polymkeric substance (P) 100 mass parts from the ratio of the polymer unit of reactive emulsifier.Aforementioned proportion, if with respect to polymkeric substance (P) 100 mass parts less than 0.5 mass parts, then becoming is difficult to obtain the stability in storage of water-based metal-surface-treating agent of the present invention, if surpass 5 mass parts, then there is the tendency that reduces in the water tolerance of resulting tunicle.About emulsifying agent, be described further in the back.
Polymkeric substance (P) as mentioned above, the polymerized unit conduct that can contain from (methyl) acrylate (A) must constitute the unit, contain from the polymerized unit of silicon-containing monomer (B), from α, the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) and/or reactive emulsifier is as optional formation unit, constitute the unit as the residue except above-mentioned polymerized unit, all contain from being selected from the polymerized unit that (methyl) alkyl acrylate that does not contain aromatic ring reaches at least a kind of (methyl) acrylate in (methyl) acrylic acid hydroxy alkyl ester.
The carbonatoms of abovementioned alkyl is preferably 1～10, and more preferably 1～6, further be preferably 1～4.In addition, the carbonatoms of hydroxyalkyl is preferably 1～10, and more preferably 1～6, further be preferably 1～4.
As above-mentioned (methyl) acrylate, particularly can enumerate: methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, the just own ester of vinylformic acid, cyclohexyl acrylate, Octyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, decyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, the methacrylic tert-butyl acrylate, the just own ester of methacrylic acid, cyclohexyl methacrylate, Octyl methacrylate, Isooctyl methacrylate, methacrylic acid-2-ethylhexyl, decyl-octyl methacrylate, methacrylic acid-2-hydroxy methacrylate, vinylformic acid-3-hydroxy propyl ester.
The manufacture method of polymkeric substance (P) is not particularly limited, and polymkeric substance (P) can use existing known method to make.For example, polymkeric substance (P) can use and polymerization starter, water, emulsifying agent and monomer is mixed together and methods such as polymeric method, monomer dropping method, pre-emulsion process are synthesized.And, can also carry out multi-stage polymerics such as seeding polymerization, hud polymerization, automatic feed polymerization and carry out the out-phase structurizing of particle.Polymerization temperature is generally 0～100 ℃, is preferably 40～95 ℃, and polymerization time is preferably 1～10 hour.
Polymerization starter is not particularly limited, and can use for example ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, the two lauroyl of peroxidation, tertbutyl peroxide etc.
In water-based metal-surface-treating agent of the present invention, polymkeric substance (P) utilizes emulsifying agent and is dispersed in the water.
Emulsifying agent can use at least a kind that is selected from reactive emulsifier and the non-reacted emulsifying agent.As reactive emulsifier, be not particularly limited, can enumerate vinylsulfonate, styrene sulfonate, methacrylic acid sulphur ethyl ester salt, alkyl allyl group sulfosuccinate, the thiazolinyl sulfosuccinate, polyoxyalkylene alkene ether vitriol (polyoxyalkylene alkenyl ethersulfate), the polyoxyalkylene alkene ether, polyxyethylated propenyl phenylate, polyxyethylated allyl phenyl ether sulfuric acid, polyoxyethylene-1-(allyloxy methyl) alkyl ether sulphate salts, α-[1-{ (allyloxy) methyl }-2-(Nonylphenoxy) ethyl]-ω-hydroxyl polyoxyethylene, alpha-sulfo-ω-(1-(alkoxyl group) methyl-2-(2-propenyloxy group) oxyethyl group)-poly-(oxygen-ethylene) salt etc.As non-reacted emulsifying agent, be not particularly limited, can enumerate higher fatty acid salt (sodium laurate, sodium oleate etc.), higher alcohol sulfate salt (lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate etc.), senior alkyl arylsulphonate (Sodium dodecylbenzene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate etc.), polyoxyethylene nonylphenol ether, ethoxylated dodecyl alcohol, Brij-721, Brij, polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyglycol distearate etc.As above-mentioned salt, can enumerate sodium salt, sylvite, ammonium salt etc.
As emulsifying agent, can only use reactive emulsifier, also can only use non-reacted emulsifying agent, can also be with two kinds and usefulness, but, preferably use reactive emulsifier from reducing the viewpoint of emulsifying agent usage quantity.
Usage quantity when only using reactive emulsifier as emulsifying agent is illustrated.Usage quantity when only using non-reacted emulsifying agent with respect to polymkeric substance (P) 100 mass parts, is preferably 3～10 mass parts, more preferably 5～8 mass parts.If less than 3 mass parts, then the stability in storage of water-based metal-surface-treating agent of the present invention becomes and is difficult to obtain, if surpass 10 mass parts, then there is the tendency that reduces in the water tolerance of resulting tunicle.And the usage quantity during with reactive emulsifier and non-reacted emulsifying agent, can be with reference to only using the usage quantity when a kind of to determine.As known from the above, as the usage quantity of emulsifying agent integral body,, be preferably 0.5～10 mass parts, more preferably 1～8 mass parts with respect to polymkeric substance (P) 100 mass parts.
Polymer dispersion liquid (emulsion or suspension liquid) or polymers soln by above-mentioned polymerization obtains can directly or after adjusting solid component concentration use as metal conditioner.
Metal conditioner of the present invention can contain softening agent (Q).
The material that has at least 1 ester bond and/or at least 1 ehter bond in the preferred molecule of softening agent (Q), more preferably be selected from 2,2,4-trimethylammonium-1, in 3-pentanediol mono isobutyrate, diethylene glycol monobutyl ether acetic ester, ethylene glycol monobutyl ether and the dipropylene glycol n-butyl ether at least a kind, further preferred 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate and/or diethylene glycol monobutyl ether acetic ester.Softening agent (Q) then can not play a role as the softening agent of polymkeric substance (P) if do not have ester bond and ehter bond, thereby not preferred.
The combined amount of softening agent (Q) with respect to polymkeric substance (P) 100 mass parts, is preferably 0.5～50 mass parts, and more preferably 2～45 mass parts further are preferably 5～40 mass parts.If above-mentioned combined amount then is difficult to show the additive effect of softening agent (Q) less than 0.5 mass parts, and consequently becoming is difficult to obtain good film-forming properties, and becomes and be difficult to obtain the good transparency of tunicle.In addition, if surpass 50 mass parts, then there is the tendency that reduces in stability in storage.
And film forming is meant membranization, is meant interfused state between dried polymkeric substance (P) particle on the microcosmic.Becoming mem stage, softening agent (Q) plays a role as the softening agent of polymkeric substance (P), promotes interparticle fusion.Consequently the diffuse-reflectance of incident light is inhibited, the transparency raising of tunicle and alkali resistance and acid resistance improve, and the cohesive force of tunicle improves, thereby processibility improves.
Water-based metal-surface-treating agent of the present invention in order to improve chemical resistant properties and/or erosion resistance, can also contain in addition other resin of polymkeric substance (P), promptly not have a resin of the two keys of C=C.As other above-mentioned resin, can enumerate the acrylic resin that do not have arbitrarily the two keys of C=C, Resins, epoxy, carbamate resins etc.As other resin, be not particularly limited, can use resin commonly used in the water-based metal-surface-treating agent, as acrylic resin, can use for example poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate, polyacrylic acid-2-ethylhexyl etc., as Resins, epoxy, can use for example bisphenol-A epoxy resin etc., as carbamate resins, can use for example hexamethylene diisocyanate, aliphatic diisocyanate and polyether glycol (polyoxyethylene glycol such as isophorone diisocyanate, polypropylene glycol, polytetramethylene glycol etc.) or the polycondensate of polyester polyol (condenses of hexanodioic acid and ethylene glycol etc.).
The combined amount of other resin with respect to polymkeric substance (P) 100 mass parts, when being acrylic resin, is preferably below 70 mass parts, below more preferably 60 quality are divided, further is below 50 mass parts; When being Resins, epoxy, be preferably below 90 mass parts, more preferably below 80 mass parts, further be preferably below 70 mass parts; When being carbamate resins, be preferably below 90 mass parts, more preferably below 80 mass parts, further be preferably below 70 mass parts.If surpass preferred range use separately, then be difficult to obtain deriving from UV resistant deterioration, alkali resistance, acid resistance, processibility and the tunicle perviousness of polymkeric substance (P).
The medium of water-based metal-surface-treating agent of the present invention is a water.
Water-based metal-surface-treating agent of the present invention, in the scope of not damaging effect of the present invention, can contain the water-soluble solvent, rust-stabilising pigment, the tinting pigment that are useful on the even paint that improves coating, are used to improve the drying property of tunicle, be used to improve, be used to improve the additives such as wax of oilness by film density with by weighting agents such as the liquid phase of film hardness or aerosils.As even paint, can use non-ionic type or cationic tensio-active agent, can enumerate polyethylene oxide or poly(propylene oxide) affixture, the acetylenediol compound etc. of polyacetylene glycol (polyacetylene glycol), as water-soluble solvent, can enumerate alcohols such as ethanol, Virahol, the trimethyl carbinol, propylene glycol, ester such as vinyl acetic monomer, N-BUTYL ACETATE class, ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) etc.
The addition of these additives adds up to solids component with respect to this surface treatment agent less than 20 quality %.
Shared ratio in the solids component of polymkeric substance (P) in water-based metal-surface-treating agent of the present invention, it is the ratio of polymkeric substance in the dry coationg (P), be preferably 10～100 quality %, more preferably 20～100 mass parts % further are preferably 30～100 mass parts %.The ratio of polymkeric substance (P) is difficult to obtain deriving from ultraviolet resistance, alkali resistance, acid resistance, processibility and the tunicle transparency of polymkeric substance (P) during less than 5 quality %.
And, in the present invention, consider in the drying process of softening agent after coating and evaporate, though thereby think that part should be residual, plasticizer-containing not in the solids component.
Minimum film-forming temperature when water-based metal-surface-treating agent of the present invention is applied to metallic substance is preferably-5～40 ℃, more preferably 0～20 ℃.If minimum film-forming temperature is lower than-5 ℃, then there is the tendency that is difficult to obtain stability in storage.If minimum film-forming temperature is higher than 40 ℃, then film forming becomes insufficient, is difficult to obtain the transparency of tunicle, and is difficult to obtain alkali resistance and acid resistance.
The pH of water-based metal-surface-treating agent of the present invention is preferably 3～12, more preferably 5～10.If pH is less than 3 or surpass 12, then be difficult to obtain the dispersion stabilization of polymkeric substance (P).
Solid component concentration in the water-based metal-surface-treating agent of the present invention is not particularly limited, but is preferably 3～50 quality %, more preferably 5～35 quality %.If less than 3 quality %, then coating may have problems, and the treatment agent cost up.If surpass 50 quality %, the tendency that then exists stability in storage to reduce.
Use the metallic substance of water-based metal-surface-treating agent of the present invention to be not particularly limited, can use iron for example, with iron as the alloy of main body, aluminium, with aluminium as the alloy of main body, copper, be alloy of main body etc. with copper, can also use the coated metal material that on any metallic substance, has carried out plating, for example steel plate galvanized.In the application of water-based metal-surface-treating agent of the present invention, most preferred material is a zinc-based metal plated steel sheet.As zinc-based metal plated steel sheet, can enumerate steel plate galvanized, zinc-plated-the nickel steel plate, zinc-plated-the iron steel plate, zinc-plated-the chromium steel plate, zinc-plated-the aluminum steel plate, zinc-plated-titanium steel plate, zinc-plated-the magnesium steel plate, zinc-plated-manganese steel plate, zinc-plated-aluminium-the magnesium steel plate, zinc-plated-Al-Si-Mg steel plate etc., can also use and in above-mentioned coating, contain cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminium, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic etc. as the steel plate of a spot of dissimilar metal element or impurity and make inorganics dispersive steel plates such as silicon-dioxide, aluminum oxide, titanium dioxide.And water-based metal-surface-treating agent of the present invention also can be applied to the above coating and the coating of other kind, for example combination such as iron plating, iron-phosphorus coating, nickel coating, cobalt coating and the multiple coating that obtains.Method for plating is not particularly limited, and can use any one method in known electrochemical plating, calorizing, vapour deposition method, compound plating method, the physical vaporous deposition etc.
Water-based metal-surface-treating agent of the present invention, be coated on the metallic substance, preferably 50～250 ℃, more preferably 70～150 ℃, further preferably carry out drying under the arrival temperature (arriving the metallic substance temperature) at 100～140 ℃, be applied to metallic substance thus.Be lower than 50 ℃ if arrive temperature, if be higher than 250 ℃, then there is the tendency of the part decomposition of the tunicle that is formed by this water-based metal-surface-treating agent in then not volatilization fully of the solvent of this water-based metal-surface-treating agent.Dried tunicle quality optimization is 0.05～5.0g/m
2, 0.2～3.0g/m more preferably
2, further be preferably 0.5～2.5g/m
2If by film quality less than 0.05g/m
2, then can not show each performance, if greater than 5.0g/m owing to can not cover the surface of this metallic substance
2, then add and produce waste material man-hour, the tendency that exists operability to reduce.
Embodiment
Below enumerate embodiments of the invention and comparative example specifically describes the present invention, but the present invention is not limited to these embodiment.
The manufacturing of polymer dispersion liquid
(1) constituent of polymkeric substance
(methyl) acrylate (A) of use below is shown.Use the contrast of vinylbenzene (St) as (methyl) acrylate (A).
A1: isobornyl acrylate
A2: isobornyl methacrylate
St: vinylbenzene (contrast)
The silicon-containing monomer (B) of use below is shown.
B1: vinyl three (methoxy ethoxy) silane
B2:3-acryloxy propyl trimethoxy silicane
B3:3-methacryloxypropyl methyl dimethoxysilane
The emulsifying agent that uses is as follows.
S1: as ェ レ ミ ノ one Le JS-2 (Sanyo Chemical Industries Co., Ltd.'s system of reactive emulsifier; Alkyl allyl group sulfosuccinate)
S2: as LN2025D (テ ィ カ Co., Ltd. system of non-reacted emulsifying agent; Sodium dodecylbenzene sulfonate)
Other monomer that uses is methyl methacrylate (MMA), ethyl acrylate (2EHA) and butyl acrylate (BA).
(2) Production Example of polymer dispersion liquid
In the four-hole boiling flask that stirrer, reflux exchanger, dropping funnel and thermometer are installed, behind the nitrogen replacement inner air, to wherein dropping into 150 mass parts ion exchanged waters and 3 mass parts ェ レ ミ ノ, one Le JS-2.In dropping funnel, add 10 mass parts isobornyl acrylate, 44.5 mass parts MMA, 37.0 mass parts BA, 1 mass parts vinyl three (methoxy ethoxy) silane and 4.5 mass parts vinylformic acid and mix, make mix monomer.Then, flask is warming up to 70 ℃ after, 10 quality % of mix monomer are dropped in the flask, drop into ammonium sulfate 0.3 mass parts then.After reaction finishes, with dripping remaining mix monomer 90 quality % in 3 hours.After dripping end the flask temperature was kept 1 hour at 75 ℃ down, obtain polymer dispersion liquid.
The manufacturing of surface treatment liquid
(1) polymkeric substance (P) composition in addition
The softening agent that uses is as follows.
Q1:2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate
Q2: diethylene glycol monobutyl ether acetic ester
Q3: ethylene glycol monobutyl ether
Q4: dipropylene glycol mono-n-butyl ether
Q5:N-N-methyl-2-2-pyrrolidone N-(contrast)
Other resin that uses is as follows.
R1: hexylene glycol type polyether-polyurethane resin
R2: bisphenol A-type polyether-polyurethane resin
(2) Production Example of surface treatment liquid
Regulate pH to 7 by ammoniacal liquor after will being cooled to 40 ℃ by the above-mentioned polymer dispersion liquid that obtains, add diethylene glycol monobutyl ether acetic ester 30 mass parts, make the surface treatment liquid of embodiment 25 as softening agent.
(3) manufacturing of surface treatment liquid
Table 1 illustrate make according to the Production Example of surface treatment liquid, as the surface treatment liquid of embodiment, table 2 illustrates surface treatment liquid as a comparative example.And, the solid component concentration of surface treatment liquid is adjusted into 30 quality %.
The preparation of test board
(1) starting material
The commercially available starting material that use illustrates below.
Hot-dip galvanizing sheet steel (GI): thickness of slab=0.8mm, plating amount=60/60 (g/m
2)
Pot galvanize-55% aluminium alloy steel plate (GL): thickness of slab=0.8mm, plating amount=150/150 (g/m
2)
(2) skimming treatment
Will be as the Off ァ ィ Application Network リ one Na 1 (registered trademark: Nihon Parkerizing Co., Ltd.'s system) be dissolved in the water of silicates alkaline defatting agent with concentration 20g/L, use gained solution under the condition of 60 ℃ of temperature, starting material to be carried out 2 minutes pre-treatment, clean 30 seconds after drying with pure water.
(3) be coated with method with being coated on the starting material after the skimming treatment, shown in the table 1 by rod so that dried tunicle amount reaches 1.5g/m as the surface treatment liquid of embodiment and the surface treatment liquid as a comparative example shown in the table 2 a kind of
2, carry out drying being up to reach under 80 ℃ of the plate temperature, make test board.
Evaluation method
(1) stability in storage
Under situation about leaving standstill in the atmosphere gas of each surface treatment liquid with above-mentioned preparation, with the evaluation of the time till gelation stability in storage at 40 ℃.
(judgement criteria)
◎: more than 6 months
More than zero: 3 month and be less than 6 months
△: more than 1 month and be less than 3 months
*: be less than 1 month
Utilize following evaluation method to estimate the performance of each test board.
(2) UV resistant deterioration
Use fluorescence ultraviolet ray dampening unit (the wetting exposure test machine of UVCON luminescent lamp ultraviolet ray), the ultraviolet ray of irradiation 365nm 4 hours, under 50 ℃ of atmosphere temperature degree, humidity 60%Rh, left standstill 2 hours then, above-mentioned condition is made as 1 circulation, implement 30 circulations, estimate the UV resistant deterioration by the tonal variation (Δ E) before and after the test.
Tone is measured and is used Color Meter ZE2000 (NIPPON DENSHOKU system, light source: halogen lamp 12V/2A) carry out.Tone in following alkali resistance and the acid proof evaluation is measured and is carried out too.
(judgement criteria)
◎：ΔE＜1
○：1≤ΔE＜3
△：3≤ΔE＜7
×：7≤ΔE
(3) alkali resistance
Dipping is 1 hour in 25 ℃ 3 quality % aqueous sodium hydroxide solutions, estimates alkali resistance by the tonal variation (Δ E) before and after the test.
(judgement criteria)
◎：ΔE＜1
○：1≤ΔE＜3
△：3≤ΔE＜7
×：7≤ΔE
(4) acid resistance
Dipping is 1 hour in 25 ℃ 3 quality % hydrochloric acid, estimates acid resistance by the tonal variation (Δ E) before and after the test.
(judgement criteria)
◎：ΔE＜1
○：1≤ΔE＜3
△：3≤ΔE＜7
×：7≤ΔE
(5) processibility
Estimate processibility by the faulted condition that utilizes universal testing machine to carry out bead (draw bead) test postevaluation surface.Drawing condition is compacting 0.5 ton of load, muscle tip radius 5mm, the high 5mm of muscle, drawing speed 5cm/ second.
(judgement criteria)
◎: not damaged
Zero: damage is arranged slightly
△: partly produce and burn trace
*: whole produces the burning trace
(6) the tunicle transparency
Change (Δ L) by the lightness before and after the surface treatment, carry out the evaluation of the tunicle transparency.Lightness is measured and is used Color Meter ZE2000 (NIPPON DENSHOKU system, light source: halogen lamp 12V/2A) carry out.
(judgement criteria)
◎：-1＜ΔL＜1
Zero :-5＜Δ L≤-1 or 1≤Δ L＜5
△ :-10＜Δ L≤-5 or 5≤Δ L＜10
*: Δ L≤-10 or 10≤Δ L
Evaluation result is shown in table 3～table 6.In table 3～table 6, ultraviolet resistance is the implication of UV resistant deterioration.By the embodiment of correspondence and comparative example more as can be known, under prerequisite situation within the scope of the invention, stability in storage, the UV resistant deterioration, alkali resistance, acid resistance, the processibility and the tunicle transparency are good, relative therewith, Tg crosses alkali resistance when hanging down, acid resistance and poor in processability, stability in storage when Tg is too high, alkali resistance, acid resistance, the processibility and the tunicle transparency are poor, in addition, using vinylbenzene to replace (methyl) acrylate (A), or use under the situation of resin with the two keys of C=C as other resin, the UV resistant deterioration is poor, in addition, replace under the situation of (methyl) acrylate (A) alkali resistance at (methyl) acrylate that uses other, acid resistance and poor in processability.In addition, by between the embodiment more as can be known, under the situation of using silicon-containing monomer (B), stability in storage reduces, but the UV resistant deterioration improves; Using α, under the situation of β-ethylenically unsaturated carboxylic acids (C), the tendency that exists UV resistant deterioration, acid resistance and the tunicle transparency to improve; Using under the situation of reactive emulsifier as emulsifying agent, comparing, can reduce the usage quantity of emulsifying agent and obtain identical effect with the situation of using non-reacted emulsifying agent; Under the situation of using preferred plasticizer, to compare with the situation of not using this softening agent, the tunicle transparency is good.
Table 1
Each scale shows mass parts
Table 2
Each scale shows mass parts
Table 3
Table 4
Table 5
Table 6
Claims (13)
1. metal conditioner, contain polymkeric substance (P), emulsifying agent and water, and polymkeric substance (P) disperseed by described emulsifying agent, have the polymerized unit of (methyl) acrylate (A) of self-drifting (I) expression in the molecule of described polymkeric substance (P), and second-order transition temperature is 0～70 ℃
In the formula (I), R1 represents hydrogen atom or methyl, and R2 represents the represented group of general formula (II),
In the formula (II), R3, R4 and R5 represent the alkyl of hydrogen atom, hydroxyl or carbonatoms 1～3 independently of each other.
2. treatment agent as claimed in claim 1 wherein, has the polymerized unit of the silicon-containing monomer (B) of self-drifting (III) expression in the molecule of polymkeric substance (P),
In the formula (III), R6, R7 and R8 represent the alkyl of hydrogen atom, hydroxyl, carbonatoms 1～3, the alkoxyl group or carbonatoms 1～3 alkoxyl group carbonatoms 1～3 alkoxyl group of carbonatoms 1～3 independently of each other, X expression (IV) or the represented group of logical formula V
In the formula V, R9 represents that hydrogen atom or methyl, R10 represent the alkylene of carbonatoms 1～12.
3. treatment agent as claimed in claim 1 wherein, has from α the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) in the molecule of polymkeric substance (P).
4. treatment agent as claimed in claim 2 wherein, has from α the polymerized unit of β-ethylenically unsaturated carboxylic acids (C) in the molecule of polymkeric substance (P).
5. treatment agent as claimed in claim 1, wherein, emulsifying agent is a reactive emulsifier, and since the form of polymer unit of autoreaction emulsifying agent be present in the polymkeric substance (P).
6. treatment agent as claimed in claim 1, wherein, except polymerized unit from (methyl) acrylate (A), it all is from being selected from the polymerized unit that (methyl) alkyl acrylate that does not contain aromatic ring reaches at least a kind of (methyl) acrylate in (methyl) acrylic acid hydroxy alkyl ester that the residue of polymkeric substance (P) constitutes the unit, and wherein the carbonatoms of alkyl or hydroxyalkyl is 1～10.
7. treatment agent as claimed in claim 5, wherein, except from the polymerized unit of (methyl) acrylate (A) and the polymerized unit from reactive emulsifier, it all is from being selected from the polymerized unit that (methyl) alkyl acrylate that does not contain aromatic ring reaches at least a kind of (methyl) acrylate in (methyl) acrylic acid hydroxy alkyl ester that the residue of polymkeric substance (P) constitutes the unit, and wherein the carbonatoms of alkyl or hydroxyalkyl is 1～10.
8. as each described treatment agent in the claim 1～7, wherein, be 0.1～50 mass parts with respect to polymkeric substance (P) 100 mass parts from the ratio of the polymerized unit of (methyl) acrylate (A).
9. as claim 2 or 4 described treatment agents, wherein, be 0.5～2.0 mass parts with respect to polymkeric substance (P) 100 mass parts from the ratio of the polymerized unit of silicon-containing monomer (B).
10. treatment agent as claimed in claim 3, wherein, the acid number of polymkeric substance (P) is 5～40mgKOH/g.
11., wherein,, contain softening agent (Q) 0.5～50 mass parts with respect to polymkeric substance (P) 100 mass parts as each described treatment agent in the claim 1～7.
12. treatment agent as claimed in claim 11, wherein, softening agent (Q) has at least 1 ester bond and/or at least 1 ehter bond in molecule.
13. treatment agent as claimed in claim 12, wherein, softening agent (Q) is for being selected from 2,2,4-trimethylammonium-1, in 3-pentanediol mono isobutyrate, diethylene glycol monobutyl ether acetic ester, ethylene glycol monobutyl ether and the dipropylene glycol n-butyl ether at least a kind.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-317368 | 2007-12-07 | ||
| JP2007317368 | 2007-12-07 | ||
| PCT/JP2008/070658 WO2009072380A1 (en) | 2007-12-07 | 2008-11-13 | Water-based metal-surface-treating agent |
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| Publication Number | Publication Date |
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| CN101874087A true CN101874087A (en) | 2010-10-27 |
| CN101874087B CN101874087B (en) | 2014-04-09 |
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|---|---|
| JP (1) | JP5314816B2 (en) |
| KR (1) | KR101265398B1 (en) |
| CN (1) | CN101874087B (en) |
| AU (1) | AU2008332500B2 (en) |
| MY (1) | MY169645A (en) |
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|---|---|---|---|---|
| CN113337812A (en) * | 2021-04-26 | 2021-09-03 | 博罗县东明化工有限公司 | Magnesium alloy conversion film enhancement treatment agent and magnesium alloy surface treatment method |
| CN115124900A (en) * | 2022-07-27 | 2022-09-30 | 厦门双瑞船舶涂料有限公司 | IBOA modified long-acting anticorrosion water-based acrylic coating and preparation method thereof |
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| CN103710169B (en) * | 2013-12-31 | 2016-01-20 | 长沙艾森设备维护技术有限公司 | A kind of aq. type deck clean-out system |
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| JP3414251B2 (en) * | 1998-03-13 | 2003-06-09 | 信越化学工業株式会社 | Silicone resin-containing emulsion composition, method for producing the same, and article having cured coating of the composition |
| JP3464609B2 (en) * | 1998-07-21 | 2003-11-10 | 新日本製鐵株式会社 | Pre-coated metal sheet with excellent blocking resistance |
| JP2000218230A (en) * | 1999-01-29 | 2000-08-08 | Nippon Steel Corp | Surface treatment of galvanized steel sheet |
| JP2000336232A (en) * | 1999-05-26 | 2000-12-05 | Daicel Chem Ind Ltd | Aqueous resin composition |
| JP2002069660A (en) * | 2000-08-28 | 2002-03-08 | Nippon Parkerizing Co Ltd | Aqueous agent for metal surface treatment without including hexa-valent chromium and metal sheet surface-treated therewith |
| JP2002361787A (en) * | 2001-06-04 | 2002-12-18 | Kansai Paint Co Ltd | High designability metal siding structure |
| JP3970595B2 (en) * | 2001-12-10 | 2007-09-05 | 綜研化学株式会社 | Thermally polymerized acrylic paint, coated metal sheet using the paint, and method for producing painted metal sheet |
| JP2004346131A (en) * | 2003-05-20 | 2004-12-09 | Toyobo Co Ltd | Polyester resin and composition |
| JP2007181984A (en) * | 2006-01-06 | 2007-07-19 | Furukawa Sky Kk | Resin-coated aluminum sheet material which is excellent in heat dissipating property, conductivity and processability |
| JP2007211079A (en) * | 2006-02-08 | 2007-08-23 | Kansai Paint Co Ltd | Design coating material for precoated metal |
| CN1944476A (en) * | 2006-10-19 | 2007-04-11 | 湖北大学 | Process for preparing fluorin, silicon, epoxide modified low surface energy acrylate emulsion for heavy anti-corrosion paint |
| CN100560626C (en) * | 2007-03-07 | 2009-11-18 | 哈尔滨工业大学 | A kind of antirust emulsion of self-crosslinked interpenetrating net polymer and preparation method thereof |
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|---|---|---|---|---|
| CN113337812A (en) * | 2021-04-26 | 2021-09-03 | 博罗县东明化工有限公司 | Magnesium alloy conversion film enhancement treatment agent and magnesium alloy surface treatment method |
| CN115124900A (en) * | 2022-07-27 | 2022-09-30 | 厦门双瑞船舶涂料有限公司 | IBOA modified long-acting anticorrosion water-based acrylic coating and preparation method thereof |
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| TWI437123B (en) | 2014-05-11 |
| JPWO2009072380A1 (en) | 2011-04-21 |
| AU2008332500B2 (en) | 2011-12-22 |
| KR20100083845A (en) | 2010-07-22 |
| MY169645A (en) | 2019-04-24 |
| KR101265398B1 (en) | 2013-05-20 |
| TW200932950A (en) | 2009-08-01 |
| JP5314816B2 (en) | 2013-10-16 |
| WO2009072380A1 (en) | 2009-06-11 |
| CN101874087B (en) | 2014-04-09 |
| AU2008332500A1 (en) | 2009-06-11 |
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